The interaction of tungsten with CeO(2)(111) layers grown on Cu(111) was studied in the temperature range between 300 and 870 K by photoelectron spectroscopy of the core levels and resonant valence band spectroscopy. The interaction was found to be very strong even at 300 K, leading to the formation of cerium tungstate Ce(6)WO(12) in which the metal atoms were in Ce(3+) and W(6+) chemical states. The growth was limited by the diffusion of W atoms into the ceria layer, so subsequent tungsten deposition led to formation of W suboxides with consecutively lower chemical oxidation states, i.e. W(4+), W(2+) and metallic W(0) with an almost negligible contribution of W(5+). Step-wise annealing of the layer showed that due to stimulated diffusion of tungsten into ceria at higher temperature, Ce(6)WO(12) was formed more easily. Larger W overlayer thicknesses needed higher annealing temperature to promote diffusion. The thickest sample studied, 1.4 nm W/CeO(2), was transformed by annealing to 870 K to the Ce(6)WO(12)/W system with a tungsten monoxide (WO) interface, whereas the rest of the tungsten was converted to the W(6 + ) oxidation state.